Halogenated anthraquinoneacridones and the process of making same



Patented Apr. 18, 1933 rm; or N YORK, N. Y., A

WALTER BRUCK, or MANNHEIM, GERMANY, AssIenoR TOGENERAL An-rLrnE worms;

con-roR 'rIoN or DELAWARE HALOGENATED ANrHnAQUINoNE omDonEsAND rnnr'nocnss orQM AxrNG s' Mn'.

No brewing. Application fil ed October 10, 1929, Seria1No:398 ,820, andjin Germany dctober 2 7, 1928.

The present invention relates to the production of anthraqulnoneacridones conta ning chlorine and'bromlne.

I have found that'anthraquinoneacridones 5 which contain bromine and chlorine, are particularlyvaluablevat dyestu-fl's and that the said bromochloroanthraquinoneacridones are very easilyobtaine'd by treating an anthraquinonea'cridone contaming one of the said halogens with a halogenating agent supplying the other halogen-. The anthraquinoneacridones containing one ofthe said halogens may be produced in any known manner, for example, synthetically by condensation of 35 a-chloranthraquinone with a halogenated anthranilic acid and ring closure to the acridone, or by the action of a halogenating agent on anthraquinoneacridones. The 'halogenation is suitably carried out in organic diluents,; such as nitrobenzene, trichlorobenzene and- V the like, and preferably with the aid ofhalogenating catalysts, such as sulphur, iodine, U

metals or metal salts. As the anthraquinoneacridones containing only one of the sald halogens employed as initial materials maybe produced by the action of a halogenating agent on anthraquinoneacridones, my invention provides also a method of producing the anthraquinoneacridones containing two dif ferent halogens in one operation by the simultaneous action of chlorinating and brominating agents.

Generally speaking the products thus obtainable are characterized by excellent fastness to light. Particularly valuable are the I products containing only a single atom of bromine and from 1 to 2 atoms of chlorine.

The following examples will further illus-. trate the nature of this invention but the I 40 invention is not restricted to these examples' The parts are by weight.

- Example 1 101 parts of monobromoanthraquinone-t acridone which is probably a mixture ofv BZS -i and Bz'5-monobromoanthra done corresponding to formulae:

nN VHNV.

Y (obtainable by treating anthraqu inoneacridone in nitrobenzene with bromine dissolved in nitrobenzene at aboutl10? to lZOcehtigrade) and 1.3 parts ofiodi'neare stirred in 780 parts ofnitrobenzene; About. 170 parts of sulphuryl chloride are then allowedtorun the' wholje is then'stirred forabout 3 hours longer at the same temperature., After cool-' ing, the productis filtered off by suction and washed with nitrobenz'ene; the crystalline filtered materialis then treated withste am and dried. Y'Analysis shows that '2 atoms of chlorine have been taken u l i l tBzo-dichloro-Blzii bromoland l.Bz3.-. di-; 'chloro-Bz5-bromoanthraquinoneacridone. i i I ,p "The product crystallizes from nitrobeniene in redviolet needles. :I The colorof the solutionin concentrated sulphuric: acid is orange red. It giyes'a Violet Vat with hydrosulphite; 011 cotton bluish red dyeings areffirstpbtained, and these'are' changed-to rediViOlet by treatment with aiboilihg solution of soap;

- g A mixture of 101 partsof monobroinoan thraquinoneacridone*and1;3 parts of iodine is stirred "with 780 parts of nitrobenz ene. Then about 73 .partsof chlorine are passed in at a temperature of from 'to; centigrade during a period of about 7 hours? in ata terii perature of from toilOOF ceI 1ti-; grade during a period o f'about 41- hours, and

quinoneacri- The product is probably of "done and 1 part of iodine, a mixture of 18 parts of bromine, parts of sulphuryl ch10 ride and 30 parts of nitrobenzene being then run into the aforesaid mixture which has lowed to cool.

36 parts of 4-chloroanthraquinoneacridone see Liebigs Annalen 381, page 22) are suspended in 850 parts of nitrobenzene. A solution of 25 parts of bromine in25 0 parts of nitrobenzene is added to thesaid suspension which has been warmed to C. The

reaction mixture'is stirred for about 2 hours at the said temperature which is then raised in the course of 2 hours to the boiling point. i The whole is then allowed to cool and the reaction product separated in the form of red violet acicular needles which are filtered i off. The reaction product may be recrystallized from trichlorobenzene and 1s a monochloro inonobromoanthraquinoneacridone according to analysis, dyeing cotton from a violet vat blue red shades.

It is probably a mixture ofl-chloro-BZ3- bromoand 4-chloro-Bz5-bromoanthraquinoneacridone.

Example 4 600 parts of nitrobenzene are added to a mixture of 32.6 parts of anthraquinoneacribeen warmed 'to about 95v C. in the course of about 1 hour. Thewhole is then stirred at the said temperature for 7 hours and alcrystalline form is adibromo-monochloroan- I thraquinoneacridone dissolving in concen-' trated'sulphuric acidto give an orange reds olution and dyeing cotton from. a violet vat blue red shades. The dyestufi may be recrystallized from trichlorobenzene;

What I'claim is;

The; product separated in initial material, and agents supplying such halogen.

3. A process of producing anthraquinoneacridones containing chlorine and bromine, which comprises causing an anthraquinoneacridone containing one of the said halogens to react in an inert organic solvent in the presence'of a halogenating catalyst with a halogenating agent selected from the group consisting of one of the said halogens which is different from that already present in the initial material, and'a'gents supplying such halogen.

4. process of producing an-thraquinoneacridones contain ng chlorine and bromine,

which comprises causingan anthraquinoneacridone to react with a chlorinating agent and a brominating agent selected from the group consistingof chlorine and'broinine and agents supplying these halogens.

5. M o nob romoanth'raquinoneacridones containing from 1 to 2 atoms of chlorine and dyeing cottonfrom vi oletivatsviolet to violet red shades.

6. 'D i c hloromonobromoantliraquinoneacridone dissolving in concentrated sulphuric acid to give an orangered solution and dyein cotton from Violet vat red violet shades. n testimony whereof I' have hereunto set WALTER BRUCK.

i my hand.

1..A process of producing .anthraquin-' v oneacri'dones containing chlorine and bro-- mine, which comprises causing an anthra-- quinoneacridone containingone of the said halogens to react with a halogenating agent selected from the group consisting of one of the said halo-gens which is diii'erent frointhat already present in the initial material, and agents supplying such halogen.

2. A process of producing anthraquinoneacridones containin'gchlorine and bromine,

which comprises causingfan anthraquinoneacridone containing one of the said halogens to react in an inert organic solvent with a halogenating agent selected from the group :consisting of one of the said halogens which is different from that already present in the 

